Process for the photo-polymerisation of cyclic olefins using a thermostable molybdenum or tungsten catalyst

ABSTRACT

A process for photocatalytic polymerisation of a cyclic olefin or of at least two different cyclic olefins in the presence of a metal compound as catalyst, which process comprises carrying out a photochemically induced ring-opening metathesis polymerisation in the presence of a catalytic amount of at least one thermostable molybdenum (VI) or tungsten (VI) compound which contains at least two methyl groups or two monosubstituted methyl groups lacking β-hydrogen atoms in the substituent and which are bonded to the metal atom. The process may be carried out by first irradiating and terminating the polymerisation by heating. The process is suitable for fabricating moulded articles, coatings and relief images.

The present invention relates to a process for the polymerisation ofcyclic olefins by photochemical ring-opening metathesis polymerisationusing catalytic amounts of a transition metal catalyst, and tocompositions comprising said olefins together with a catalytic amount ofsaid catalyst.

Thermally induced ring-opening metathesis polymerisation using catalyticamounts of metal catalysts has been known for some considerable time andis widely described in the literature (q.v. inter alia K. J. Ivin,Olefin Metathesis, Academic Press, London, 1983). Such polymers areprepared industrially and are commercially available. However,photochemically induced ring-opening metathesis polymerisation is onlylittle known and so far commercial utilities have not resulted.

U.S. Pat. No. 4 060 468 discloses an olefin metathesis polymerisationwhich is carried out by charging a two-component mixture of a metal saltselected from tungsten, molybdenum, rhenium and tantalium salts and asubstituted phenol or benzyl alcohol as co-catalysts to a reactor withthe olefin monomer, and then irradiating the entire reaction mixturewith UV light The only olefins mentioned are cyclic and acylichydrocarbons without functional groups or substituents. The separatestorage of the catalyst components and the process step of mixing thecatalyst components directly before the actual reaction make the knownprocess technically complicated and troublesome.

In Tetrahedron Letters No. 52, pp. 4589-4592 (1977), C. Tanielan et al.describe the catalyst system W(CO)₆ /CCl₄, which, after irradiation withUV light, can be used for the metathesis polymerisation of cyclopenteneand norbornene. Metal carbonyls are volatile and toxic, so that theiruse requires elaborate protective measures for physiological reasons. Inaddition, a free radical addition reaction is observed as competingreaction to form monomeric 1-chloro-2-trichlormethylcycloolefins.

It is known from H. H. Thoi et al., Journal of Molecular Catalysis, 15(1982), pp. 245-270, that a tungsten pentacarbonylcarbene complex offormula ##STR1## is a thermal catalyst for the ring-opening metathesispolymerisation of dimethyl norbornene and, together with phenylacetylene as co-catalyst, is also a photocatalyst system for the samepolymerisation. This catalyst system has the serious shortcoming that,as ready-for-use formulation, it has only poor storage stability, thecarbonyl compound is physiologically unacceptable, and the tolerance tofunctional groups in cycloolefins is too low.

J. Feldmann et al describe in Progress in Inorganic Chemistry, Vol. 39,pp. 3-73, Edited by Stephen J. Lippard (1991), molybdenum and tungstenalkylidene complexes which, singly, are only poor, but together withLewis acids, are effective, thermal catalysts for the polymerisation ofcycloolefins.

In WO 93/13171 are described one component catalysts on the basis ofcarbonyl containing Mo- and W-compounds and Ru- or Os-compounds with apolyene ligand for the ring-opening photometathesis of strainedcycloolefines. With this catalysts are obtained storage stablecompositions under exclusion of light.

N. A. Petasis et al. mention in J. Am. Chem. Soc. 115 (1993), pages7208-7214 the thermal ring-opening photometathesis of norbornene inusing (cyclopentadienyl)₂ Ti CH₂ -Si(CH₃)₃ !₂ as thermal catalysts. Aphotoinitiating activity is not mentioned.

The known catalysts which can be activated photochemically thus mainlyrequire a co-catalyst, for which reason the quality of the resultantpolymers can vary greatly owing to the chosen nature and sequence of thereactants.

Polymers obtained from cyclic olefins by photochemical ring-openingmetathesis polymerisation can only be prepared by the known processeswith a great deal of trouble and in an economically unsatisfactorymanner. Particular disadvantages are the poor stability, which onlypermits the components to be mixed directly before the preparation, thelack of tolerance to functionalised cyclic olefins, and the necessity ofusing two components as catalyst system. Hence for technical, economicand environmental reasons there is a need to provide an improved andgenerally useful process for the preparation of polymers from cyclicolefins by photochemical ring-opening metathesis polymerisation.

It has been found that compositions of cycloolefins and a singlecomponent catalyst are photochemically polymerisable if the compositioncontains a molybdenum or tungsten compound in a high state of oxidation,in which at least two alkyl groups lacking β-hydrogen atoms are bondedto the metal atom. Surprisingly, these thermally stable compounds havebeen found to be effective catalysts for the photochemically inducedring-opening metathesis polymerisation and, despite the photochemicalreactivity, the storage stability of mixtures of cycloolefins and themolybdenum or tungsten compounds is retained.

It has also surprisingly been found that the above catalysts act asthermal catalysts even after brief irradiation in the presence ofcycloolefins, so that the photochemical and thermal polymerisation canbe carried out together.

In one of its aspects, the invention relates to a process forphotocatalytic polymerisation of a cyclicolefin, or of at least twodifferent cyclic olefins, in the presence of a metal compound ascatalyst, which process comprises carrying out a photochemically inducedring-opening metathesis polymerisation in the presence of a catalyticamount of at least one thermostable molybdenum (VI) or tungsten (VI)compound that contains at least two methyl groups or two monosubstitutedmethyl groups lacking β-hydrogen atoms in the substituent and which arebonded to the metal atom. Substituent means the substituted methylgroup.

The cyclic olefins can be monocyclic or polycyclic fused ring systems,typically containing two to four rings which are unsubstituted orsubstituted and containing hetero atoms such as O, S, N or Si in one ormore than one ring, and/or fused aromatic or heteroaromatic rings suchas o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. Thecyclic rings may contain 3 to 16, preferably 3 to 12 and, mostpreferably, 3 to 8, ring members. The cyclic olefins may contain furthernon-aromatic double bonds, preferably 2 to 4 such additional doublebonds, depending on the size of the ring. The ring substituents arethose that are inert, i.e. that do not impair the chemical stability andthe thermostability of the molybdenum or tungsten compounds.Thermostability means within the scope of this invention that thephotocatalytically active molybdenum or tungsten compounds, when heated,form no active species for the ring-opening metathesis polymerisation.For example, it has been found that, after heating these catalysts, withexclusion of air, to 110° C. for 24 hours, no such active species aredetectable. The catalyst cannot, for example, at room temperature toslightly elevated temperature, e.g. +40° C., initiate any ring-openingmetathesis polymerisation over a period of weeks to months, withexclusion of light, and during this time less than 0.2% by weight ofmonomer is reacted. The thermostabiity can be determined by storing anethanolic solution containing 20% by weight of monomer and 0.33% byweight of tungsten or molybdenum catalyst at 50° C. for 96 hours in thedark, and any polymer formed (detectable from the turbidity) is not morethan 0.2% by weight and preferably not more than 0.1% by weight.

If the cyclic olefins contain more than one double bond, for example 2to 4 double bonds, crosslinked polymers are formed. This feature is alsoobserved when using (norbornenehydroxymethyl)norbornenecarboxylic acidesters of formula ##STR2##

In a preferred embodiment of the novel process, the cycloolefins are offormula I ##STR3## wherein Q₁ is a radical having at least one carbonatom which, together with the --CH═CQ₂ -- group, forms an at least3-membered alicyclic ring which may contain one or more hetero atomsselected from the group consisting of silicon, phosphorus, oxygen,nitrogen and sulfur; and which radical is unsubstituted or substitutedby halogen, ═O, --CN, --NO₂, R₁ R₂ R₃ Si--(O)_(u) --, --COOM, --SO₃ M,--PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₂₀alkyl, C₁ -C₂₀ hydroxyalkyl C₁ -C₂₀ haloalkyl, C₁ -C₆ cyanoalkyl, C₃ -C₈cycloalkyl, C₆ -C₁₆ aryl, C₇ -C₁₆ aralkyl, C₃ -C₆ heterocycloalkyl, C₃-C₆ heteroaryl, C₄ -C₁₆ heteroaralkyl or R₄ --X--; or in which twoadjacent C atoms are substituted by --CO--O--CO-- or --CO--NR₅ --CO--;or in which an aromatic or heteroaromatic ring, which is unsubstitutedor substituted by halogen, --CN, --NO₂, R₆ R₇ R₈ Si--(O)_(u) --, --COOM,--SO₃ M, PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁-C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀ hydroxyalkyl, C₁ -C₆ cyanoalkyl,C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl, C₇ -C₁₆ aralkyl, C₃ -C₆heterocycloalkyl, C₃ -C₁₆ heteroaryl, C₄ -C₁₆ heteroaralkyl or R₁₃ --X₁--, is fused to adjacent carbon atoms of the alicyclic ring;

X and X₁ are each independently of the other --O--, --S--, --CO--,--SO--, --SO₂ --, --O--C(O)--, --C(O)--O--, --C(O)--NR₅ --, --NR₁₀--C(O)--, --SO₂ --O-- or --O--SO₂ --;

R₁, R₂ and R₃ are each independently of one another C_(1-C) ₁₂ alkyl, C₁-C₁₂ perfluoroalkyl, phenyl or benzyl;

R₄ and R₁₃ are each independently of the other C₁ -C₂₀ alkyl, C_(1-C) ₂₀haloalkyl, C₁ -C₂₀ hydroxyaLkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl or C₇-C₁₆ aralkyl;

R₅ and R₁₀ are each independently of the other hydrogen, C₁ -C₁₂ alkyl,phenyl or benzyl, the alkyl groups in turn being unsubstituted orsubstituted by C₁ -C₁₂ alkoxy or C₃ -C₈ cycloalkyl;

R₆, R₇ and R₈ are each independently of one another C₁ -C₁₂ alkyl, C₁-C₁₂ perfluoroalkyl, phenyl or benzyl;

M is an alkali metal and

M₁ is an alkaine earth metal; and

u is 0 or 1;

and the alicyclic ring formed with Q₁, may contain further non-aromaticdouble bonds;

Q₂ is hydrogen, C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₁₂ alkoxy,halogen, --CN or R₁₁ --X₂ --;

R₁₁ is C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀ hydroxyalkyl, C₃ -C₈cycloalkyl, C₆ -C₁₆ aryl or C₇ -C₁₆ aralkyl;

X₂ is --C(O)--O-- or --C(O)--NR₁₂ --;

R₁₂ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl;

and the above mentioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl,aralkyl and heteroaralkyl groups are unsubstituted or substituted by C₁-C₁₂ alkyl, C₁ -C₁₂ alkoxy, --NO₂, --CN or halogen, and the hetero atomsof the above mentioned heterocycloalkyl, heteroaryl and heteroaralkylgroups are selected from the group consisting of --O--, --S--, --NR₉ --and --N═; and

R₉ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl.

Other olefins which are capable of metathesis can be used concurrentlyin the process of this invention, for example in amounts of up to 40 mol%, preferably 0.01 to 30 mol %, and particularly preferably 0.1 to 20mol %, based on the total amount of cycloolefins and olefins present.

Olefins which are capable of metathesis, and which the novelpolymerisable mixtures of formula I may additionally comprise, can beused for crosslitiing or for regulating the molecular weight. Examplesof suitable olefins are cyclooctadiene or cyclooctatriene or compoundshaving the following structures: ##STR4## Furthermore, compounds such as2-butene-1,4-diol, as described in Feast, W. J., Harison, B. J. Mol.Catal. 65, 63 (1991), or 1-hexene (rearrangements) are also suitable.

If the compounds of the formula I contain a centre of asymmetry, thenthe compounds may be obtained in the form of optical isomers. Some ofthe compounds of formula I may occur in tautomeric forms (for exampleketo-enol tautomerism). If an aliphatic C═C double bond is present,geometric isomerism (E-form and Z-form) can also occur. In addition,exo-endo configurations are also possible. Formula I thus embraces allpossible stereoisomers which exist in the form of enantiomers,tautomers, diastereomers, E/Z isomers or mixtures thereof.

In the definition of the substituents, the alkyl, alkenyl and alkynylgroups may be straight-chain or branched, as may also the alkyl moietyor each alkyl moiety of alkoxy, alkylthio, alkoxycarbonyl and otheralkyl-containing groups. These alkyl groups preferably contain 1 to 12,more particularly 1 to 8, and, most preferably, 1 to 4, carbon atoms.These alkenyl and alkynyl groups preferably contain 2 to 12, moreparticularly 2 to 8, and, most preferably, 2 to 4, carbon atoms.

Alkyl typically comprises methyl, ethyl, isopropyl, n-propyl, n-butyl,isobutyl, sec-butyl, tert-butyl and the various isomeric pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosylradicals.

Hydroxyalkyl typically comprises hydroxymethyl, hydroxyethyl,1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl,1-hydroxy-iso-butyl, 1-hydroxy-sec-butyl, 1hydroxy-tert-butyl and thehydroxy forms of the various isomeric pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.

Haloalkyl typically comprises fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyland halogenated, in particular fluorinated or chlorinated, alkanes, forexample the isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl,tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl and eicosyl radicals.

Alkenyl typically comprises propenyl, isopropenyl, 2-butenyl, 3-butenyl,isobutenyl, n-penta-2,4dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl,n-dodec-2-enyl, iso-dodecenyl, n-octadec-2-enyl and n-octadec-4-enyl.

Cycloalkyl is preferably C₅ -C₈ cycloalkyl, most preferably C₅ - or C₆cycloalkyl. Typical examples are cyclopropyl, dimethylcyclopropyl,cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl andcyclooctyl.

Cyanoalkyl typically comprises cyanomethyl (methylnitrile), cyanoethyl(ethylnitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl,1-cyano-iso-butyl, 1-cyano-sec-butyl, 1-cyano-tert-butyl and thedifferent isomeric cyanopentyl and cyanohexyl radicals.

Aralkyl preferably contains 7 to 12 carbon atoms and, most preferably, 7to 10 C atoms. Aralkyl may typically be benzyl, phenethyl,3-phenylpropyl, α-methylbenzyl, phenbutyl and α,α-dimethylbenzyl.

Aryl preferably contains 6 to 10 carbon atoms and may typically bephenyl, pentalene, indene, naphthalene, azulene and anthracene.

Heteroaryl preferably contains 4 or 5 carbon atoms and one or two heteroatoms selected from the group consisting of O, S and N. heteroaryl maytypically be pyrrole, furan, thiophene, oxazole, thioazole, pyridine,pyrazine, pyrimidine, pyridazine, indole, purine and quinoline.

Heterocycloalkyl preferably contains 4 or 5 carbon atoms and one or twohetero atoms selected from the group consisting of O, S and N. It maytypically be oxirane, azirine, 1,2oxathiolane, pyrazoline, pyrrolidine,piperidine, piperazine, morpholine, tetrahydrofuran andtetrahydrothiophene.

Alkoxy is typically methoxy, ethoxy, propoxy, isopropoxy, n-butoxy,isobutoxy, sec-butoxy and tert-butoxy.

Alkali metal in the context of this invention will be understood asmeaning lithium, sodium, potassium, rubidium and caesium, preferablylithium, sodium and potassium.

Alkaline earth metal in the context of the present invention will beunderstood as meaning beryllium, magnesium, calcium, strontium andbarium, preferably magnesium and calcium.

In the above definitions, halogen will be understood as meaning fluoro,chioro, bromo and iodo. Fluoro, chloro and bromo are the preferredmeanings.

Particularly suitable compounds of the formula I for the process of theinvention are those in which Q₂ is hydrogen.

Further compounds of formula I which are preferred for thepolymerisation are those in which the alicyclc ring that Q₁ formstogether with the --CH═CQ₂ -- group contains 3 to 16, more particularly3 to 12 and, most preferably, 3 to 8, ring atoms, which ring system maybe monocyclic, bicyclic, tricyclic or tetracyclic.

The inventive process can be carried out with particular advantage withthose compounds of the formula I, wherein

Q₁ is a radical having at least one carbon atom which, together with the--CH═CQ₂ -- group, forms a 3- to 20-membered alicyclic ring which maycontain one or more hetero atoms selected from the group consisting ofsilicon, oxygen, nitrogen and sulfur; which radical is unsubstituted orsubstituted by halogen, ═O, --CN, --NO₂, R₁ R₂ R₃ Si--(O)_(u) --,--COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃(M₁)_(1/2), C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₁-C₄ cyanoalkyl, C₃ -C₆ cycloalkyl, C₆ -C₁₂ aryl, C₇ -C₁₂ aralkyl, C₃ -C₆heterocycloalkyl, C₃ -C₁₂ heteroaryl, C₄ -C₁₂ heteroaralkyl or R₄ --X--;or two adjacent carbon atoms in said radical Q₁ are substituted by--CO--O--CO-- or --CO--NR₅ --CO--; or an aromatic or heteroaromatic ringwhich is unsubstituted or substituted by halogen, --CN, --NO₂, R₆ R₇ R₈Si--, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃(M₁)_(1/2), C_(1-C) ₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂ hydroxyalkyl,C₁ -C₄ cyanoalkyl, C₃ -C₆ cycloalkyl, C₆ -C₁₂ aryl, C₇ -C₁₂ aralkyl, C₃-C₆ heterocycloalkyl, C₃ -C₁₂ heteroaryl, C₄ -C₁₂ hetroaralkyl or R₁₃--X₁ -- can be fused to adjacent carbon atoms;

X and X₁ are each independently of the other --O--, --S--, --CO--,--SO--, --SO₂ --, --O--C(O)--, --C(O)--O--, --C(O)--NR₅ --, --NR₁₀--C(O)--, --SO₂ --O-- or --O--SO₂ --; and R₁, R₂ and R₃ are eachindependently of one another C₁ -C₆ alkyl, C₁ -C₆ perfluoroalkyl, phenylor benzyl;

M is an alkali metal and M₁ is an alkaline earth metal;

R₄ and R₁₃ are each independently of the other C₁ -C₁₂ alkyl, C₁ -C₁₂haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₂ aryl or C₇-C₁₂ aralkyl;

R₅ and R₁₀ are each independently of the other hydrogen, C₁ -C₆ alkyl,phenyl or benzyl, the alkyl groups in turn being unsubstituted orsubstituted by C₁ -C₆ alkoxy or C₃ -C₆ cycloalkyl;

R₆, R₇ and R₈ are each independently of one another C₁ -C₆ alkyl, C₁ -C₆perfluoroalkyl, phenyl or benzyl;

u is 0 or 1;

and the alicyclic ring formed with Q₁ may contain further non-aromaticdouble bonds;

Q₂ is hydrogen, C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₆ alkoxy,halogen, --CN or R₁₁ --X₂ --;

R₁₁ is C₁ -C₁₂ alkyl, C₁ -C₁₂ halogalkyl, C₁ -C₁₂ hydroxyalkyl, C₃ -C₆cycloalkyl, C₆ -C₁₂ aryl or C₇ -C₁₂ aralkyl;

X₂ is --C(O)--O-- or --C(O)--NR₁₂ --; and

R₁₂ is hydrogen, C₁ -C₆ alkyl, phenyl or benzyl;

and the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl andheteroaralkyl groups are unsubstituted or substituted by C₁ -C₆ alkyl,C₁ -C₆ alkoxy, --NO₂, --CN or halogen, and the hetero atoms of theheterocycloalkyl, heteroaryl and heteroaralkyl groups are selected fromthe group consisting of --O--, --S--, --NR₉ -- and --N═; and

R₉ is hydrogen, C₁ -C₆ alkyl, phenyl or benzyl.

Among this group, those compounds of formula I are preferred wherein

Q₁ is a radical having at least one carbon atom which, together with the--CH═CQ₂ --group, forms a 3- to 10-membered alicyclic ring which maycontain a hetero atom selected from the group consisting of silicon,oxygen, nitrogen and sulfur, and which radical is unsubstituted orsubstituted by halogen, --CN, --NO₂, R₁ R₂ R₃ Si--, --COOM, --SO₃ M,--PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₆alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ hydroxyallyl, C₁ -C₄ cyanoalkyl, C₃ -C₆cycloalkyl, phenyl, benzyl or R₄ --X--; or an aromatic or heteroaromaticring which is unsubstituted or substituted by halogen, --CN, --NO₂, R₆R₇ R₈ Si--, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2),--PO3(M₁)_(1/2), C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ hydroxyalkyl, C₁-C₄ cyanoalkyl, C₃ -C₆ cycloalkyl, phenyl, benzyl or R₁₃ --X₁ -- can befused to adjacent carbon atoms;

R₁, R₂ and R₃ are each independently of one another C₁ -C₄ alkyl, C₁ -C₄perfluoroalkyl, phenyl or benzyl;

M is an alkali metal and M₁ is an alkaline earth metal;

R₄ and R₁₃ are each independently of the other C₁ -C₆ alkyl, C₁ -C₆haloalkyl, C₁ -C₆ hydroxyalkyl or C₃ -C₆ cycloalkyl; --O--, --S--,--CO--, --SO--or --SO2--;

X and X₁ are each independently of the other --O--, --S--, --CO--,--SO-- or --SO₂ --; R₆, R₇ and R₈ are each independently of one anotherC₁ -C₄ alkyl, C₁ -C₄ perfluoroalkyl, phenyl or benzyl; and

Q₂ is hydrogen.

The process of this invention is particularly suitable for thepolymerisation of norbornenes and norbornene derivatives. Among thesenorbornene derivatives, those compounds are especially preferred whichconform to formula II ##STR5## wherein X₃ is --CHR₁₆ --, oxygen orsulfur, R₁₄ and R₁₅ are each independently of the other hydrogen, --CN,trifluoromethyl, (CH₃)₃ Si--O--, (CH₃)₃ Si-- or --COOR₁₇ ; and

R₁₆ and R₁₇ are each independently of the other hydrogen, C₁ -C₁₂ alkyl,phenyl or benzyl; or to formula III ##STR6## wherein X₄ is --CHR₁₉ --,oxygen or suilir;

R₁₉ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl; and

R₁₈ is hydrogen, C₁ -C₆ alkyl or halogen; or to formula IV ##STR7##wherein X₅ is --CHR₂₂ --, oxygen or sulfur;

R₂₂ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl;

R₂₀ and R₂₁ are each independently of the other hydrogen, CN,trifluoromethyl, (CH₃)₃ Si--O--, (CH₃)₃ Si-- or --COOR₂₃ ; and

R₂₃ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl;

or to formula V ##STR8## wherein X₆ is --CHR₂₄ --, oxygen or sulfur;

R₂₄ is hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl;

Y is oxygen or ##STR9## and R₂₅ is hydrogen, methyl, ethyl or phenyl.

The following compounds of formula I are particularly suitable for thepolymerisation process of this invention: ##STR10##

The molybdenum and tungsten compounds to be used in the practice of thisinvention may be those which contain one metal atom or two metal atomslinked through a single. double or triple bond. The compounds contain atleast two, more particularly two to six and, most preferably, two tofour methyl groups or monosubstituted methyl groups lacking β-hydrogenatoms as metal-ligand bonds. The other valencies of molybdenum andtungsten are preferably saturated with thermostable neutral ligands (thedefinition of thermostability has been stated at the outset). Thisligand without β-hydrogen atoms preferably has the formula VII

    --CH.sub.2 --R                                             (VII),

wherein R is H, --CF₃, --CR₂₆ R₂₇ R₂₈, --SiR₂₉ R₃₀ R₃₁, unsubstituted orC₁ -C₆ alkyl- or C₁ -C₆ alkoxy-substituted C₆ -C₁₆ aryl or C₄ -C₁₅heteroaryl containing 1 to 3 hetero atoms selected from the groupconsisting of O, S and N; and

R₂₆, R₂₇ and R₂₈ are each independently of one another C₁ -C₁₀ alkylwhich is unsubstituted or substituted by C₁ -C₁₀ alkoxy, or R₂₆ and R₂₇have this meaning and R₂₈ is C₆ -C₁₀ aryl or C₄ -C₉ heteroaryl which isunsubstituted or substituted by C₁ -C₆ alkyl or C₁ -C₆ alkoxy; and

R₂₉, R₃₀ and R₃₁ are each independently of one another C₁ -C₆ alkyl,C₅ - or C₆ cycloalkyl, or unsubstituted phenyl or benzyl or phenyl orbenzyl each substituted by C₁ -C₆ alkyl or C₁ -C₆ alkoxy.

R₂₆ to R₃₁ in the significance of alkyl may be linear or branched andcontain preferably 1 to 8 and, most preferably, 1 to 4, carbon atoms.R₂₈ to R₃₁ defined as aryl are preferably phenyl or naphthyl.

R in defined in formula VII as aryl is preferably phenyl or naphthyl. Rdefined in formula VII as heteroaryl is preferably pyridinyl, furanyl,thiophenyl or pyrrolyl.

Preferred substituents for R₂₆ to R₃₁ within the scope of thedefinitions are methyl, ethyl, methoxy and ethoxy. Exemplarysubstituents R₂₆ to R₃₁ have been cited previously in connection withthe compounds formula I.

In a preferred embodiment of the invention, the group R in formula VIIis H, --C(CH₃)₃, --C(CH₃)₂ C₆ H₅, unsubstituted phenyl or phenyl whichis substituted by methyl, ethyl, methoxy or ethoxy, --CF₃, or--Si(CH₃)₃.

The other 1 to 4 valencies of the Mo(VI) and W(VI) atoms can besaturated with identical or different ligands selected from the groupconsisting of ═O, ═N--R₃₃, secondary amines containing 2 to 18 carbonatoms, R₃₂ O-- or R₃₂ S--, halogen, cyclopentadienyl or bridgedbiscylopentadienyl, tridentate monoanionic ligands, or neutral ligandssuch as arenes, olefins, ethers, nitriles, CO and tertiary phosphinesand amines, wherein the R₃₂ substituents independently of each other areunsubstituted or C₁ -C₆ alkoxy- or halogen-substituted linear orbranched C₁ -C₁₈ alkyl, C₅ -- or C₆ cycloalkyl which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy or halogen, or phenyl whichis unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen, or benzyl which isunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen, or phenylethyl; and R₃₃ isunsubstituted or C₁ -C₆ alkoxy-substituted linear or branched C₁ -C₁₈alkyl, C₅ - or C₆ cycloalkyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ alkoxy or halogen, phenyl which is unsubstituted orsubstituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆alkoxyethyl, di(C₁ -C₆ -alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkylor halogen, or benzyl which is unsubstituted or substituted by C₁ -C₆alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl orhalogen, or phenylethyl.

Secondary amines are preferably those of formula R₃₄ R₃₅ N--, whereinR34 and R₃₅ are each independently of the other linear or branched C₁-C₁₈ alkyl, C₅ - or C₆ cycloalkyl, unsubstituted or C₁ -C₆ alkoxy- orhalogen-substituted benzyl or phenylethyl, (C₁ -C₆ alkyl)₃ Si or, takentogether, are tetramethylene, pentamethylene or 3-oxapentan-1,5-diyl.Alkyl preferably contains 1 to 12 and, most preferably, 1 to 6, carbonatoms. Typical examples are dimethylamino, diethylamino,di-n-propylamino, diisopropylamino, di-n-butylamino, methylethylamino,dibenzylamino, benzylmethyereino, diphenylamino, phenylmethylamino anddi(tdriethylsilyl)amino.

Halogen as ligand or substituent is preferably F and, most preferably,Cl.

Cyclopentadienyl may be unsubstituted or substituted by one to five C₁-C₄ alkyl groups, preferably methyl, or --Si(C₁ -C₄ alkyl), preferably--Si(CH₃)3. Bridged cyclopentadienyls are preferably those of formulaR₃₆ --A--R₃₆, wherein R₃₆ is cyclopentadienyl which is unsubstituted orsubstituted by one to five C₁ -C₄ alkyl groups, preferably methyl, or--Si(C₁ -C₄ alkyl), preferably --Si(CH₃)₃, and A is --CH₂ --, --CH₂--CH₂ --, --Si(CH₃)₂ --, --Si(CH₃)₂ --Si(CH₃)₂ -- or --Si(CH₃)₂--O--Si(CH₃)₂ --.

Suitable arenes are typically aromatic hydrocarbons or fusedhydrocarbons containing 6 to 18 carbon atoms, or 5- or 6memberedheterocycles or fused heterocycles containing one hetero atom selectedfrom the group consisting of O, S and N and containing 4 to 17 carbonatoms. Typical examples are benzene, naphthalene, naphthacene, pyrene,pyridine, quinoline and thiophene.

Olefins as neutral ligands may typically be open-chain or cyclic mono-or diolefins containing 2 to 8 carbon atoms. Typical examples areethene, propene, butene butadiene, hexene, hexadiene, cyclohexadiene andcyclooctadiene.

Ethers suitable as neutral ligands may be dialkyl ethers containing 2 to8 carbon atoms or cyclic ethers containing 5 or 6 ring members. Typicalexamples are diethyl ether, methyl ethyl ether, diethyl ether,di-n-propyl ether, diisopropyl ether, di-n-butyl ether, ethylene glycoldimethyl ether, tetrahydrofuran and dioxane.

Nitriles suitable as neutral ligands may be aliphatic or aromaticnitriles containing 1 to 12, preferably 1 to 8, carbon atoms. Typicalexamples are acetonitrile, propionitrile, butyl nitrile, benzonitrileand benzyl nitrile.

Tertiary amines and phosphines suitable as neutral ligands may be thosecontaining 3 to 24, preferably 3 to 18, carbon atoms. Typical examplesare trimethylamine and trimethylphosphine, triethylamine andtriethylphosphine, tri-n-propylamine and tri-n-propylphosphine,tri-n-butylarnine and tri-n-butylphosphine, triphenylamine andtri-phenylphosphine, tricyclohexylamine and tricyclohexylphosphine,phenyldimethylamine and phenyldimethylphosphine, benzyldimethylamine andbenzyldimethylphosphine, 3,5-dimethylphenyldimethylamine and3,5-dimethylphenyldimethylphosphine.

The tridentate monoanionic ligands may typically behydro(trispyrazol-1-yl)borates or alkyl(trispyrazol-1-yl)borates, whichare unsubstituted or substituted by 1 to 3 C₁ -C₄ alkyl groups q.v. S.Trofimenko, Chem. Rev., 93, pp. 943-980 (1993)!, or C₅ (R'₅)Co(R₃₇ R₃₈P═O!.sup.⊖, wherein R' is H or methyl and R₃₇ and R₃₈ are eachindependently of the other C₁ -C₄ alkyl, C₁ -C₄ alkoxy or phenyl q.v. W.Klaui, Angew. Chem. 102, pp. 661-670 (1990)!.

Halogen as substituent of R₃₂ and R₃₃ is preferably fluoro and, mostpreferably, chloro. The substituents alkyl, alkoxy or alkoxy inalkoxymethyl or alkoxyethyl preferably contain 1 to 4 and, mostpreferably, 1 or 2 carbon atoms. Typical examples are methyl, ethyl, n-and isopropyl, n-, iso- and tert-butyl, methoxy, ethoxy, n- andisopropoxy and n-, iso- and tert-butoxy.

R₃₂ and R₃₃ contain as alkyl preferably 1 to 12, more particularly 1 to8 and, most preferably, 1 to 4, carbon atoms. Branched alkyl ispreferred. Typical examples of of R₃₂ are methoxy, ethoxy, n- andisopropoxy, n-, iso- and tert-butoxy, hexafluoroisopropoxy and hexa- andperfluorobutoxy.

Typical examples of substituted phenyl and benzyl for R₃₂ and R₃₃ arep-methylphenyl or benzyl p-fluorophenyl or p-chlorophenyl orp-chlorobenzyl, p-ethylphenyl or ethylbenzyl, p-n- or isopropylphenyl orp-n- or isopropylbenzyl, p-isobutylphenyl or p-isobutylbenzyl,3-methylphenyl or 3-methylbenzyl, 3-isopropylphenyl or 3-isopropylbenzyl3,5-dimethylphenyl or 3,5-dimethylbenzyl, 3,5-isopropylphenyl or3,5-isopropylbenzyl, 3,5-n- or -tert-butylphenyl and 3,5-n- or-tert-butylbenzyl. R₃₃ is most preferably unsubstituted or C₁ -C₄ alkyl-or C₁ -C₄ alkoxy-substituted phenyl.

In a preferred embodiment of the invention, the molybdenum and tungstencompounds are in particular compounds of formula VIII and also offormulae VIIIa, VIIIb and VIIIc, ##STR11## wherein Me is Mo(VI) orW(VI),

at least two, preferably 2 to 4, of the substituents R₃₉ to R44 are aradical --CH₂ --R of formula VII, R is H, --CF₃, --CR₂₆ R₂₇ R₂₈, --SiR₂₉R₃₀ R₃₁, unsubstituted or C₁ -C6alkyl- or C₁ -C₆ alkoxy-substituted C₆-C₆ aryl or C₄ -C₁₅ heteroaryl containing 1 to 3 hetero atoms selectedfrom the group consisting of O, S and N;

R₂₆, R₂₇ and R₂₈ are each independently of the other C₁ -C₁₀ alkyl whichis unsubstituted or substituted by C₁ -C₁₀ alkoxy, or R₂₆ and R₂₇ havethis meaning and R₂₈ is C₆ -C₁₀ aryl or C₄ -C₉ heteroaryl which isunsubstituted or substituted by C₁ -C₆ alkyl or C₁ -C₆ alkoxy; and R₂₉,R₃₀ and R₃₁ are each independently of one another C₁ -C₆ alkyl, C₅ - orC₆ cycloalkyl, or unsubstituted or C₁ -C₆ alkyl- or C₁ -C₆alkoxy-substituted phenyl or benzyl;

two each of the remaining substituents R₃₉ to R₄₄ are ═O or ═N--R₃₃, andR₃₃ is unsubstituted or C₁ -C₆ alkoxy-substituted linear or branched C₁-C₁₈ alkyl, unsubstituted or C₁ -C₆ aLkyl-, C₁ -C₆ alkoxy- orhalogen-substituted C₅ - or C₆ cycloalkyl, unsubstituted phenyl orphenyl which is substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen, or benzyl or phenylethyleach of which is unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen; and/or

the remaining substituents R₃₉ to R₄₄ are secondary amino containing 2to 18 carbon atoms, R₃₂ O-- or R₃₂ S--, halogen, cyclopentadienyl orbridged biscylopentadienyl or a neutral ligand, wherein the R₃₂substituents are each independently of the other unsubstituted or C₁ -C₆alkoxy- or halogen-substituted linear or branched C₁ -C₁₈ alkyl,unsubstituted or C₁ -C₆ alkyl-, C₁ -C₆ alkoxy or halogen-substitutedC₅ - or C₆ cycloalkyl, unsubstituted phenyl or phenyl which issubstituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆alkoxyethyl, di(C₁ -C₆ -alkyl)amino, di(C₁ -C₆ -alkyl)amino-C₁ -C₃ alkylor halogen, or benzyl or phenylethyl each of which is substituted by C₁-C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl orhalogen

With respect to R and R₂₆ to R₃₃, the preferred meanings previouslygiven apply.

In a particularly preferred embodiment of the process of this invention,molybdenum and tungsten compounds of formula VIII are used, wherein

a) R₃₉ to R₄₄ are a radical of formula VII --CH₂ --R, or

b) R₃₉ and R₄₀ are a radical of formula VII --CH₂ --R, R₄₁ and R₄₂together are a radical ═N--R₃₃, and R₄₃ and R₄₄ together are R₃₂ --O--or halogen, or

c) R₄₃ and R₄₄ together and R₄₁ and R₄₂ together are the radical═N--R₃₃, and R₃₉ and R₄₀ are a radical of formula VII --CH₂ --R,

and R, R₃₂ and R₃₃ have the meanings given above. With respect to R, R₃₂and R₃₃, the preferred meanings given above apply.

Among the compounds of formula VIIIc, those compounds are especiallypreferred in which R₃₉, R₄₀ and R₄, are a radical of formula VII, whichradical is most preferably --CH₂ --Si(C₁ -C₄ akyl)₃.

In the process of this invention it is most especially preferred to usemolybdenum and tungsten compounds of formulae IX, IXa or Ixb, ##STR12##wherein Me is Mo(VI) or W(VI),

R is H, --C(CH₃)₃, --C(CH₃)₂ --C₆ H₅, --C₆ H₅ or --Si(C₁ -C₄ alkyl)₃,

R₃₃ is phenyl or phenyl which is substituted by 1 to 3 C₁ -C₄ alkyl orC₁ -C₄ alkoxy groups,

R₄₁ is unsubstituted or fluoro-substituted linear or, preferably,branched C₁ -C₄ alkoxy, and

R₄₂ has the same meaning as R₄₁ or is F, Cl or Br. R₄₁ is mostpreferably branched alkoxy or branched alkoxy which may be partially orcompletely fluorinated, typically isopropoxy, iso- and tert-butoxy,hexafluoropropoxy and nonafluoropropoxy. R₄₂ is preferably Cl.

Typical examples of molybdenum and tungsten compounds are:

Mo₂ CH₂ Si(CH₃)₃ !₆, W(═N--C₆ H₅)(OCH(CH₃) 2)(Cl) (CH₂ Si(CH₃)3)!₂,

W(═N--C₆ H₅)(OCH(CF₃)2) (CH₂ Si(CH₃)₃)!₂,

Mo(═N--3,5-diisopropylC₆ H₅)₂ (CH₂ C(CH₃) ₂ --C6H₅)!₂,

Mo(═N--3,5-diisopropylC₆ H₅)₂ (CH₂ --C₆ H₅)!₂, Mo(═N--3,5-dimethylC₆H₅)₂ (CH₂ --C₆ H₅)!₂,

Mo(═N--3,5-dimethylC₆ H₅)₂ (CH₃)₂ (tetrahydrofuran),

(CH₃)₃ SiCH_(2!) ₃ Mo.tbd.Mo CH₂ Si(CH₃)₃ !₃, W(═NC₆ H₅) CH₂ Si(CH₃)₃!Cl.

The molybdenum and tungsten compounds used in the process of thisinvention are known or can be prepared by known and analogous methodsstarting from metal halides and Grignard reactions q.v. inter alia F.Hug et al. J. Chem. Soc., Chem. Commun., page 1079 (1971) or R. R.Schrock et al., J. Am. Chem. Soc., Vol. 112, page 3875 (1990)!.

The inventive process can be carried out in the presence of an inertsolvent. A particular advantage of the inventive process is that, ifliquid monomers are used, the process can be carried out without asolvent. Inert means that the choice of solvent will depend on thereactivity of the molybdenum and tungsten compounds, for example thatprotic polar solvents are not used if substitution reactions, such asreplacement of halogen by alkoxy, are to be expected.

Suitable inert solvents are typically protic polar and aprotic solvents,which can be used by themselves or in mixtures of at least two solvents.Examples of such solvents are: ethers (dibutyl ether, tetrahydrofuran,dioxane, ethylene glycol monomethyl or dimethyl ether, ethylene glycolmonoethyl or diethyl ether, diethylene glycol diethyl ether andtriethylene glycol dimethyl ether), halogenated hydrocarbons (methylenechloride, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane and1,1,2,2-tetrachloroethane), carboxylates and lactones (ethyl acetate,methyl propionate, ethyl benzoate, 2-methoxyethyl acetate,γ-butyrolactone, δ-valerolactone, pivalolactone), carboxamides andlactams (N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, tetramethylurea, hexamethyl phosphoric triam,γ-butyrolactam, ε-caprolactaon, N-methylpyirolidone,N-acetylpyrrolidone, N-methylcaprolactam), sutfoxides (dimethylsulfoxide), sulfones (dimethyl sulfone, diethyl sulfone, triethylenesulfone, tetraethylene sulfone), tertiary amines (N-methylpiperidine,N-methylmorpholine), aliphatic and aromatic hydrocarbons, for examplepetroleum ether, pentane, hexane, cyclohexane, methylcyclohexane,benzene or substituted benzenes (chiorobenzene, o-dichlorobenzene,1,2,4-trichiorobenzene, nitrobenzene, toluene, xylene) and nitrfles(acetonitrile, propionitrile, benzonitrile, phenylacetonitrile).Preferred solvents are aprotic polar and non-polar solvents.

Preferred solvents are aliphatic and aromatic hydrocarbons and mixturesof such solvents.

It is to be particularly highlighted that that the compositions used inthe practice of this invention comprising a n unsubstituted or substituted cycloolefin and catalyst are often insensitive to oxygen,thereby permitting storage and also the reaction to be carried outwithout an inert gas. It is, however, advisable to exclude atmosphericmoisture, i.e. to use dry reaction and storage conditions.

The monomers of formula I and catalysts used for the inventive processcan be stored separately as well as together as mixture, as the catalysthas a particularly high stability. The mixture can be stored prior tothe photochemical polymerisation as ready-for-use formulation, which isadvantageous for the large-scale industrial application of the inventiveprocess. Owing to its high photosensitivity, the formulation is storedin particular under UV light, preferably with exclusion of atmosphericmoisture.

In another of its aspects, the invention relates to a photopolymerisablecomposition comprising a cyclic olefin, or at least two different cyclicolefins, and a catalytically effective amount of at least onethermostable molybdenum (VI) or tungsten (VI) compound which contains atleast two methyl groups or two monosubstituted methyl groups lackingβ-hydrogen atoms in the substituent and which are bonded to the metalatom.

The inventive composition may contain formulation assistants, suitablythose compounds listed above as solvents. Known formulation assistantsare plasticisers, dyes, pigments, fillers, reinforcing fillers,lubricants and mould release agents.

It is not necessary in the inventive process to maintain the irradiationof the reaction mixture over the entire duration of the reaction. Oncethe polymerisation has been photochemically initiated, the furtherreaction course proceeds by itself even in the dark. The irradiationtime will depend on the type of light source employed. It is preferredto use UV lasers or UV lamps in the inventive process. Irradiation ofthe catalyst can be effected before, during and also after the additionof the monomers.

Suitable irradiation times are from one minute to 8 hours, in particularfrom 5 minutes to 4 hours. The sequence of the addition of monomers andcatalyst is not critical. The monomer can either be initially introducedinto the reactor or added after introduction of the catalyst. Likewise,the catalyst can be irradiated beforehand and then added to the monomer.Furthermore, the solution comprising catalyst and monomer can also beirradiated.

The inventive process is preferably carried out at room temperature toslightly elevated temperature. An increase in temperature serves toincrease the reaction rate. Only in exceptional cases do the catalyststhemselves initiate a thermal polymerisation. Therefore mainly aphotopolymerisation takes place at the temperatures chosen for thecatalysis. It should be mentioned, however, that the catalysts can beconverted into thermoactive catalysts by sufficient irradiation.

It is preferred to carry out the inventive process in the temperaturerange from -20° to +110° C.

A particular and surprising advantage of the inventive process is thatthe molybdenum and tungsten compounds employed act as thermal catalystsafter irrdiation. This feature results in the possibility of continuingand terminating the polymerisation after a brief irradiation time byapplying heat, thereby affording economic and technical advantages indifferent fields in the fabrication of moulded objects or coatings. Thecombined process is particularly suitable for the preparation ofthermoplastics.

The invention further relates to a process for the photocatalyticpolymerisation of a cyclic olefin, or at least two different cyclicolefins, in the presence of a metal compound as catalyst, which processcomprises

a) initially irradiating the cycloolefins in the presence of a catalyticamount of at least one thermostable molybdenum (VI) or tungsten (VI)compound which contains at least two methyl groups or twomonosubstituted methyl groups lacking β-hydrogen atoms in thesubstituent and which are bonded to the metal atom; or irradiating acatalytic amount of at least one thermostable molybdenum (VI) ortungsten (VI) compound which contains at least two methyl groups or twomonosubstituted methyl groups lacking β-hydrogen atoms in thesubstituent and which are bonded to the metal atom, without a solvent orin an inert solven, and then mixing the catalyst with at least onecycloolefin; and

b) terminating the polymerisation by heating and without irradiation.

The preferences deflned above apply to process stage a). The irradiationtime essentially depends on the desired reaction procedure. A briefirradiation is chosen if, for example, the polymerisation is to be onlyinitiated by irradiation and terminated by heating. Brief may be anirradiation time of up to 60 seconds, preferably 5 to 60 seconds and,most preferably, 10 to 40 seconds. A longer irradiation time may bechosen if, for example, the polymerisation is to be carried out mainlyby irradiation and the final polymerisation is to be terminated only bysubsequent heating.

Heating in process stage b) may be a reaction temperature in the rangefrom 50° to 200° C., preferably from 50° to 150° C. and, mostpreferably, from 70° to 120° C.

Catalytic amounts within the scope of this invention preferably mean anamount of 0.001 to 20 mol %, more particularly 0.01 to 15 mol % and,most preferably, 0.1 to 10 mol %, based on the amount of monomer,

A further object of the invention is a process for the preparation ofthermal catalysts for the ring-opening metathesis polymerisation ofcyclic olefins, which comprises irradiating a thermostable molybdenum(VI) or tungsten (VI) compound that contains at least two methyl groupsor two monosubstituLed methyl groups lacking β-hydrogen atoms in thesubstituent and which are bonded to the metal atom, without a solvent orin a solvent.

Cyclohexene usually cannot be homopolymerised by olefin metathesis.Those skilled in the art are familiar with this exception, which isdescribed, inter alia, in K. J. Ivin, T. Saegusa, Ring-OpeningPolymerisadon Yolume 1, page 139, Elsevier Applied Science Publishers,London and N.Y.

By the inventive process radiation-cured oligomers and polymers can beprepared having identical or different structural units of formula IX##STR13## wherein Q₁ and Q2 are as defined for formula I.

The preferences defined above apply to these polymers. They can behomopolymers or copolymers having a random distribution of thestructural units, or block polymers. They can have an average molecularweight (Mw) of, for example, 500 to 2,000,000 dalton, preferably 1000 to1,000,000 dalton (determined by GPC in comparison with a polystyrenestandard of narrow distribution).

Thermoplastical materials for the fabrication of moulded articles of alltypes, coatings and relief images can be prepared by the processaccording to the invention.

The polymers of this invention can have very different properties,depending on the monomer used. Some are distinguished by a very highoxygen permeability, low dielectric constant, good heat stability andlow water absorption. Others have outstanding optical properties, forexample high transparency and low refractive indices. The low shrinkageis furthermore to be highlighted. They can therefore be used in widelydifferent industrial fields.

The compositions of the invention are distinguished by superior bondingstrength to the surfaces of substrates. The coated materials are alsodistinguished by very good surface smoothness and gloss. Among the goodmechanical properties, the low shrinkage and high impact strength are tobe singled out for special mention, as well as the heat resistance. Easymould removal and good resistance to solvents also merit mention.

These polymers are suitable for the production of medical equipment,implants or contact lenses; for the production of electronic components;as binders for paints; as photocurable compositions for modelconstruction or as adhesives for bonding to substrates having lowsurface energy (for example Teflon, polyethylene and polypropylene), andas a photopolymerisable composition in stereolithography. Thecompositions of the invention can also be used for the production ofpaints by photopolymerisation, for which utility clear (transparent) andeven pigmented compositions to be used. Either white or colouredpigments can be used. The production of moulded objects of all types bythermoplastic shaping processes may also be mentioned.

The photocurable compositions of the invention are particularly suitablefor the production of protective layers and relief images. The inventionfurthermore relates to a variant of the process of the invention for theproduction of coated materials or relief images on substrates,comprising applying a composition of cyclic olefin, catalyst and, insome cases, solvent, as a layer to a substrate, for example by dipping,brushing, casting, rolling, knife-coating or spin-coating processes,removing the solvent, if used, and irradiating the layer to effectpolymerisation, or irradiating the layer through a photo-mask and thenremoving non-irradiated portions with a solvent. Surfaces of substratescan be modified or protected or, for example, printed circuits, printingplates or printing rollers can be produced by this process. In theproduction of printed circuits, the compositions odf the invention canalso be used as solder resists. Other possible utilities are theproduction of screen printing masks and use as radiation-curing printinginks for offset, screen and flexographic printing.

The present invention further relates to a substrate which is coatedwith an oligomer or polymer prepared according to the invention andwhich comprises a crosslinking agent. These materials are suitable forthe production of protective coatings or relief images by irradiation(usually through a photomask) and subsequent development with a solvenlSuitable crosslining agents which may be present in the materials in anamount of 0.01 to 20% by weight, are preferably organic bisazides, moreparticularly the commercially available2,6bis(4azidobenzylidene)4methylcyclohexanone.

The invention further relates to a coated substrate having appliedthereto a layer of at least one cyclic olefm which contains a catalyticamount of at least one thermostable molybdenum (VI) or tungsten (VI)compound that contains at least two methyl groups or two monosubstitutedmethyl groups lacking β-hydrogen atoms in the substituent and which arebonded to the metal atom.

The invention likweise relates to a coated substrate having thereon aradiation-cured layer of at least one cyclic olefin.

Suitable substrates are typically those of glass, minerals, ceramics,plastics, wood, metals, metal oxides and metal nitrides. The layerthicknesses will essentially depend on the desired use, and may be 0.1to 1000 μm, preferably 0.5 to 500 μm, most preferably 1 to 100 μm. Thecoated materials have superior bonding strength and good thermal andmechanical properties.

The coated materials can be prepared by known methods such as brushing,knife-coating, and casting methods such as curtain coating orspin-coating.

Particularly good coating results are obtained by using for thephotometathesis polymerisation cycloolefins that additionally containthree and preferably one further double bond and which, within the scopeof the invention, constitute fused ring systems, or if they have theformula ##STR14##

The following Examples illustrate the invention in more detail. Thelight source used is a 200 W mercury medium-pressure UV lamp (Osram HBO200 W/2, supplied by Spindler & Hoyer, Gottingen) or a UV laser(Coherent 300 Argon Laser).

EXAMPLE 1: Polymerisation of norbornene

1 ml of a 0.5% solution of W(═NC₆ H₅) OC(CH₃)₃ !(Cl) (CH₂ Si(CH₃)₃ ₂ (=5mg) in toluene is charged to a Schlenk reactor. Then 6 ml of a 10%solution of norbornene in toluene are added and the reactor is closed.With stirring, the mixture is irradiated with a UV laser (0.5 watt) for5 minutes. After about 15 seconds a rise in viscosity is observed. Thereaction is discontinued after 5 minutes by addition of one drop ofbenzaldehyde and the reaction mixture is poured into 100 ml of ethanol.The precipitated polymer is filtered, washed with ethanol and then driedunder vacuum. The polymer is obtained in quantitative yield andcharacterised by gel permeation chromatography GPC; solventtetrahydrofuran; the number average (M_(n)) and weight average (M_(w))molecular weights are determined relative to polystyrene referencestandards! and ¹ H-NMR (Bruker 300 MHz; solvent CDCl₃): M_(n) =88 000g/mol (88 k), M_(w) =340 000 g/mol (340 k); the content of cis-doublebond is 90%.

An identical experiment without exposure at 45° C. shows no rise inviscosity and no polymer precipitates after addition of ethanol.

EXAMPLE 2:

The procedure of Example 1 is repeated, except for the further additionof 8 mg (0.036 mmol) of 2,6-di-(tertiary-butyl)-p-cresol. The sameresults are obtained as in Example 1, i.e. the polymerisation is notadversely affected by phenolic antioxidants. It is therefore possible toincorporate antioxidants as processing and protective stabilisers in thepolymers during the polymerisation.

EXAMPLE 3: Production of a Moulded Object by Stereolithography

An apparatus is used with which a three-dimensional object is producedfrom cubes of differing thickness connected to one another by strands bymeans of layered polymerisation using a focused computer-controlledlaser beam (argon laser, 351 nm). A mixture of 99% by weight ofexo,exo-dicyclopentadiene and 1% by weight of W(═NC₆ H₅) OC(CH₃)₃ !(Cl)(CH₂ Si(CH₃)₃ !₂ are used. A mechanically stable moulded objectcharacterised by excellent freedom from stress is obtained at anirradiation intensity of 20-60 mJ/cm² and with a laser beam penetrationdepth of 0.1-0.2 mm.

EXAMPLE 4: Determination of Shrinkage

The mixture of Example 2 is applied in a layer thickness of 50 μm and adimension of 6 mm to a glass slide which is bonded to a silver-coatedcover glass. The shrinkage caused by the polymerisation results inwarping of the cover glass. The warp can be determinedinterferometrically in a Michelson interferometer by a helium-neonlaser. The irradiation is made with an argon UV laser at 351 nm and atan intensity of 0.2 W/cm². After irradiation, the layer thickness ismeasured and the absolute shrinkage is calculated as a function of theirradiated energy. The shrinkage after irradiation for 30 seconds (6J/cm²) is only 1 to 2%, whereas commercial photopolymer formulationsunder the same conditions exhibit a shrinkage of 5 to 8%.

EXAMPLES 5 to 23:

The procedure of Example 1 is repeated. The process conditions andresults are shown in Table 1. The following catalysts are used:

A=W(N-phenyL) OC(CH₃)₃ ! CH₂ Si(CH₃)₃ !₂ Cl

B=W(N-phenyL) OCCH₃ (CF₃)2!₂ CH₂ Si(CH₃)₃ !₂

C=W(N-2,6-dimethylphenyl)(3,5-dimethylphenyl-O) CH₂ Si(CH₃)₃ !₂ Cl

D=W(N-2,-dimethylphenyl)₂ (CH₂ -phenyl)₂

E=Mo(N-2,6-dimethylphenyl)₂ (CH₂ -phenyl)₂

F=Mo(N-2,6diisipropylphenyl)₂ CH₂ --C(CH₃)₂ phenyl!₂

G= (CH₃)₃ SiCH₂ !₃ MoMo CH₂ Si(CH₃)₃ !₃

H=W(NC₆ H₅)(3,5-dimethylphenyl-O) CH₂ Si(CH₃)₃ !₂ Cl

I=Mo(N-2,6-diisipropylphenyl)₂ (CH₂ -phenyl)2

J=Mo(N-2,6-dimethylphenyl)₂ (CH₃)₂ ·(tetrahydrofuran)

K=W(NC₆ H₅) CH₂ Si(CH₃)₃ !₃ Cl

The following monomers are used: ##STR15##

EXAMPLES 24-30:

These examples are carried out as in examples 5-23. The results areshown in Table 2.

Key to Tables 1 and 2:

¹)after reprecipitation in CHCl₃ /EtOH,

²) RT=room temperature

³) argon UV laser (0.5 W)

⁴) after reprecipitation in toluene/methanol

Key to Tables 3 to 5:

⁵)2,6-di-tert-butyl-4-methylphenol

⁶)impact strength (Charpy)

⁷)after crosslinking at 250° C.

EXAMPLES 31 to 39: Mechanical Properties of Castings

Standard castings for determining mechanical properties are fabricatedfrom the photopolymerisable compositions containing a catalyst and whichare listed in Table 2 and polymerised by irradiation and then subjectedto an optional thermal postcure. The radiation sources are (a) aself-constructed UV oven with 4 X 40 W R-UAV lamps TL, K 40 W/10/R and2×20 W TL 20 W/05 (Philips) at a distance of about 25 cm, and (b) a 200W mercury medium-pressure UV lamp (OsramF HBO 200 W/2). The curingconditions are indicated in Table 3. Modulus of elasticity (tensiletest), fracture strength and flexural elongation are determined inaccordance with ISO 527/66 (Type 2). The notched impact strength isdetermined according to ISO 179/82, Method C, and the impact strength isdetermined according to ISO 179/2D (Charpy method); the modulus ofelasticity (flexural test) is determined with an Instrone machine. Thecontact angle is determined with a microscope goniometer. The Shore Dhardness is determined with a commercially available Shore D apparatus;swelling is determined by immersing the casting in toluene at roomtemperature and measuring the weight increase of the dried specimen as afunction of the time.

The following monomers are used: ##STR16##

The results are reported in Tables 3 to 5.

                                      TABLE 1                                     __________________________________________________________________________                                  Holding-time be-                                                                             Molecular                        Example                                                                            Monomer;                                                                           Catalyst;                                                                          Solvent;                                                                             Exposure                                                                              fore processing;                                                                         Yield                                                                             weight (GPC,                     No.  amount                                                                             amount                                                                             amount time at 25° C.                                                                 temperature                                                                              (%) g/mol)                           __________________________________________________________________________    5    1; 10g                                                                             A; 100 mg                                                                          (without)                                                                            10 min  1 h; 80° C.                                                                       100 crosslinked                      6    1; 0.3 g                                                                           A; 6 mg                                                                            toluene; 1 ml                                                                        (ohne Belichtung)                                                                     14 h; 45° C.                                                                      0   --                               7    2; 1 g                                                                             A; 5 mg                                                                            toluene; 10 ml                                                                       2 min   3 Min; RT.sup.2)                                                                         60.1.sup.1)                                                                       M.sub.n = 500k                                                                M.sub.w = 2000k                  8    2; 0.3 g                                                                           A; 6 mg                                                                            toluene; 1 ml                                                                        5 min   14 h; 45° C.                                                                      100 M.sub.n = 270k                                                                M.sub.w = 1900k                  9    2; 0.3 g                                                                           B; 6 mg                                                                            toluene; 1 ml                                                                        5 min   14 h; 45° C.                                                                      61.8                                                                              crosslinked                      10   2; 0.3 g                                                                           C; 6 mg                                                                            toluene; 1 ml                                                                        5 min   2 h; 45° C. u. 48 h;                                                              68.5                                                                              crosslined                       11   2; 0.3 g                                                                           D; 6 mg                                                                            toluene; 1 ml                                                                        5 min   2 h; 45° C. u 48 h;                                                               0.8 crosslinked                      12   2; 0.3 g                                                                           E; 6 mg                                                                            toluene; 1 ml                                                                        5 min   14 h; 45° C.                                                                      36.4                                                                              M.sub.n = 100k                                                                M.sub.w = 150k                   13   2; 0.5 g                                                                           F; 15 mg                                                                           toluene; 5 ml                                                                        10 min  14 h; 50° C.                                                                      21.0                                                                              --                               14   2; 0.6 g                                                                           G; 4 mg                                                                            hexane; 6 ml                                                                         5 min.sup.3)                                                                          2 h; RT    21.7                                                                              M.sub.n = 3,7k                                                                M.sub.w = 5,3k                   15   2; 0.3 g                                                                           G; 6 mg                                                                            toluene; 1 ml                                                                        5 min   14 h; 45° C.                                                                      43.0                                                                              M.sub.n = 100k                                                                M.sub.w = 480k                   16   3; 0.82 g                                                                          A; 5 mg                                                                            toluene; 10 ml                                                                       2 min   5 min; RT  26.2                                                                              crosslinked                      17   3; 0.3 g                                                                           A; 6 mg                                                                            toluene; 1 ml                                                                        5 min   14 h; 45° C.                                                                      2.8 crosslinked                      18   3; 0.3 g                                                                           D; 6 mg                                                                            toluene; 1 ml                                                                        5 min   2 h; 45° C. u. 48 h;                                                              0.3 --                               19   3; 0.3 g                                                                           E; 6 mg                                                                            toluene; 1 ml                                                                        5 min   14 h; 45° C.                                                                      64.6                                                                              crosslinked                      20   3; 0.3 g                                                                           G; 6 mg                                                                            toluene; 1 ml                                                                        5 min   14 h; 45° C.                                                                      21.7                                                                              crosslinked                      21   4; 0.67 g                                                                          D; 30 mg                                                                           toluene; 10 ml                                                                       5 min   14 h; RT   93.9                                                                              crosslinked                      22   5; 1 g                                                                             A; 5 mg                                                                            toluene; 10 ml                                                                       5 min   15 min; RT 17.2                                                                              M.sub.n = 4k                                                                  M.sub.w = 8k                     23   6; 0.3 g                                                                           A; 6 mg                                                                            (without)                                                                            5 min   14 h; 45° C.                                                                      2.6 crosslinked                      __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________                                  Holding-time be-                                                                             Molecular                        Example                                                                            Monomer;                                                                           Catalyst;                                                                          Solvent;                                                                             Exposure                                                                              fore processing;                                                                         Yield                                                                             weight (GPC,                     No.  amount                                                                             amount                                                                             amount time at 25° C.                                                                 temperature                                                                              (%) g/mol)                           __________________________________________________________________________    24   2; 0.1 g                                                                           H; 4 mg                                                                            toluene; 5 ml                                                                        10 min  3 h; 50° C., 48 h RT                                                              100 M.sub.n = 780k                   25   2; 0.61 g                                                                          I; 3 mg                                                                            toluene; 5 ml                                                                        10 min  3 h; 50° C., 48 h RT                                                              6   M.sub.n = 18,1K                  26   2; 0.32 g                                                                          J; 3 mg                                                                            toluene; 5 ml                                                                        10 min  3 h; 50° C., 48 h RT                                                              38  M.sub.n = 100k                                                                M.sub.w = 430k                   27   2; 0.29 g                                                                          K; 2 mg                                                                            toluene; 5 ml                                                                        10 min  3 h; 50° C., 48 h RT                                                              100 M.sub.n = 110k                                                                M.sub.w = 700k                   28   7; 1.7 g                                                                           B; 10 mg                                                                           (without)                                                                            10 min  14 h; 60° C.                                                                      79.4.sup.4)                                                                       180k                             29   8; 1.54 g                                                                          B; 10 mg                                                                           (without)                                                                             1 min  14 h; RT   27.9.sup.4)                                                                       40k                              30   8; 1.54 g                                                                          A; 10 mg                                                                           (without)                                                                             1 min  14 h; RT   1.9.sup.4)                                                                        110                              __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                        Ex.            Cata-   Curing     Shrinkage                                                                            Density                              No.   Monomer  lyst    conditions (%)    (g/cm.sup.3)                         ______________________________________                                        31    1        A, 1.2  15 min UV(a) RT,                                                                         6.7    1.05                                                % by wt 90 min 50° C.                                   32    1        A, 1.0  10 min UV(a) RT,                                                                         6.7    1.05                                                5 by wt 1 h 80° C.                                      33    1        A, 1.4  30 min UV(a) RT,                                                                         4.9    1.03                                                5 by wt 40 min 50° C.                                                          30 min 80° C.                                   34    1        A, 0.7% 4 h UV(a) RT,                                                         by wt   1 h 80° C.,                                                            1 h 100° C.,                                                           30 min 120° C.                                  35    1        B, 1.0% 2 h UV(a) RT,                                                                            5.7    1.04                                                by wt   30 min 50° C.,                                                         45 min 80° C.,                                                         45 min 100° C.,                                 36    1/BHT.sup.5)                                                                           B, 1.0% 2 h UV(a) RT,                                                (1%)     by wt   30 min 80° C.,                                                         30 min 100° C.,                                                        30 min 120° C.                                  37    9        A, 0.7% 30 min UV(a) RT,                                                      by wt   1 h 80° C.                                      38    1 (84%   B, 1.0% 2 h UV(a) RT,     1.03                                       by wt);  by wt   30 min 50° C.                                         3 (16%           45 min 80° C.                                         by wt)           45 min 100° C.                                  39    1 (81%   B, 1.0% 2 h UV(a) RT,     1.02                                       by wt);  by wt   30 min 50° C.,                                        3 (19%           45 min 80° C.,                                        by wt)           45 min 100° C.,                                                        45 min 130° C.                                  ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                     Modulus                                                                       of elasti-        Flexural                                                                             Modulus of                                           city      Fracture                                                                              elonga-                                                                              elasticity                                   Tg      Tensile test                                                                            strength                                                                              tion   Flexural test                           Ex.  (°C.)                                                                          (N/mm.sup.2)                                                                            (N/mm.sup.2)                                                                          (%)    (N/mm.sup.2)                            ______________________________________                                        31   30      384 ± 15                                                                             5.5     2.0 ± 0.5                                                                         207                                     32   85                               1654                                    33   90      1923 ± 26                                                                            41.8 ± 1.3                                                                         6.0 ± 0.8                                   34                                                                            35   121     1918 ± 20                                                                            31.8 ± 1.3                                                                         1.9 ± 0.1                                                                         1560                                    36   130                                                                      37   62                                                                       38   123     1669      30.8    2.3    1830                                    39   113     1815 ± 11                                                                            39.6 ± 1.5                                                                         2.9 ± 0.4                                   ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                              Notched im-                                                                   pact strength               Shore D                                                                             Contact                               Ex.   (Charpy)  Swelling in                                                                             Crosslinking                                                                          hard- angle                                 No.   (kJ/m.sup.2)                                                                            toluene   density ness  with water                            ______________________________________                                        31    29.2 ± 1.1                                                                           230%              64-70 65-72°                         32              190%      ca. 7%  65    65-72°                         33    24.2 ± 3.0                                                                           130%                                                          34              450%                                                          35    2.84 ± 0.55.sup.6)                                                                   1300-1600%                                                                              ca. 0.4%                                                                              80                                          36              >1400%                                                        37              52%                                                           38    3.21 ± 0.10.sup.6)                                                                   700%      ca 1%   77                                                          (236%).sup.7)                                                                           (ca 14%).sup.7)                                     39    17.7 ± 10.1.sup.6)                                                                   220%              81                                          ______________________________________                                    

What is claimed is:
 1. A process for photocatalytic polymerization of acyclic olefin or of at least two different cyclic olefins in thepresence of a metal compound as catalyst, which process comprisescarrying out a photochemically induced ring-opening metathesispolymerization in the presence of a catalytic amount of at least onethermostable molybdenum (VI) or tungsten (VI) compound that contains atleast two methyl groups or two monosubstituted methyl groups lackingβ-hydrogen atoms in the substituent which are bonded to the metal atom.2. A process according to claim 1, wherein the cyclic olefins arecondensed systems containing two to four rings and which areunsubstituted or substituted and contain hetero atoms selected from thegroup consisting of O, S, N and Si in one or more than one ring, andwhich contain one or more than one fused aromatic or heteroaromaticring.
 3. A process according to claim 2, wherein the rings contain 3 to16 ring atoms.
 4. A process according to claim 3, wherein the ringscontain 3 to 12 ring atoms.
 5. A process according to claim 2, whereinthe cyclic olefins contain further non-aromatic double bonds.
 6. Aprocess according to claim 1, wherein the cycloolefins have the formulaI ##STR17## wherein Q₁ is a radical having at least one carbon atomwhich, together with the --CH═CQ₂ -- group, forms an at least 3-memberedalicyclic ring which may contain one or more hetero atoms selected fromthe group consisting of silicon, phosphorus, oxygen, nitrogen andsulfur, andselected from the group consisting of silicon, phosphorus,oxygen, nitrogen and sulfur, and which radical is unsubstituted orsubstituted by halogen, ═O, --CN, --NO₂, R₁ R₂ R₃ Si--(O)_(U) --,--COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃(M₁)_(1/2), C₁ -C₂₀ alkyl, C₁ -C₂₀ hydroxyalkyl C₁ -C₂₀ haloalkyl, C₁-C₆ cyanoalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl, C₇ -C₁₆ aralkyl, C₃ -C₆heterocycloalkyl, C₃ -C₁₆ heteroaryl, C₄ -C₁₆ heteroaralkyl or R₄ --X--;or in which two adjacent C atoms are substituted by --CO--O--CO-- or--CO--NR₅ --CO--; or in which an aromatic or heteroaromatic ring, whichis unsubstituted or substituted by halogen, --CN, --NO₂, R₆ R₇ R₈Si--(O)_(u) --, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃(M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₂₀ hydroxyalkyl, C₁ -C₆ cyanoalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₆ aryl, C₇-C₁₆ aralkyl, C₃ -C₆ heterocycloalkyl, C₃ -C₁₆ heteroaryl, C₄ -C₁₆heteroaralkyl or R₁₃ --X₁ --, is fused to adjacent carbon atoms of thealicyclic ring; X and X₁ are each independently of the other --O--,--S--, --CO--, --SO--, --SO₂ --, --O--C(O)--, --C(O)--O--, --C(O)--NR₅--, --NR₁₀ --C(O)--, --SO₂₋₋ O-- or --O--SO₂ --; R₁, R₂ and R₃ are eachindependently of one another C₁ -C₁₂ alkyl, C₁ -C₁₂ perfluoroalkyl,phenyl or benzyl; R₄ and R₁₃ are each independently of the other C₁ -C₂₀alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀ hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆-C₁₆ aryl or C₇ -C₁₆ aralkyl; R₅ and R are each independently of theother hydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl, the alkyl groups inturn being unsubstituted or substituted by C₁ -C₁₂ alkoxy or C₃ -C₈cycloalkyl; R₆, R₇ and R₈ are each independently of one another C₁ -C₁₂alkyl, C₁ -C₁₂ perfluoroalkyl, phenyl or benzyl; M is an alkali metaland M₁ is an alkaline earth metal; and u is 0 or _(1;) and the alicyclicring formed with Q₁ may contain further non-aromatic double bonds; Q₂ ishydrogen, C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₁₂ alkoxy, halogen,--CN or R₁₁ --X₂ --; R₁₁ is C₁ -C₂₀ alkyl, C₁ -C₂₀ haloalkyl, C₁ -C₂₀hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆ --C₁₆ aryl or C₇ -C₁₆ aralkyl; X₂ is--C(O)--O-- or --C(O)--NR₁₂ --; R₁₂ is hydrogen, C₁ -C₂ alkyl, phenyl orbenzyl.
 7. A process according to claim 6, wherein the alicyclic ringthat Q₁ forms together with the --CH═CQ₂ -- group contains ₃ to ₁₆ ringatoms, which ring system may be monocyclic, bicyclic, tricyclic ortetracyclic.
 8. A process according to claim 6, wherein Q₂ in formula Iis hydrogen.
 9. A process according to claim 6, wherein in formula IQ₁is a radical having at least one carbon atom which, together with the--CH═CQ₂ -- group, forms a 3- to 20-membered alicyclic ring which maycontain one or more hetero atoms selected from the group consisting ofsilicon, oxygen, nitrogen and sulfur, which radical is unsubstituted orsubstituted by halogen, ═O, --CN, --NO₂, R₁ R₂ R₃ Si--(O)_(u) --,--COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃(M₁)_(1/2), C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₁-C₄ cyanoalkyl, C₃ -C₆ cycloalkyl, C₆ -C₁₂ aryl, C₇ -Cl₂ aralkyl, C₃ -C₆heterocycloalkyl, C₃ -C₁₂ heteroaryl, C₄ -C₁₂ heteroaralkyl or R₄ --X--;or two adjacent carbon atoms in said radical Q₁ are substituted by--CO--O--CO-- or --CO--NR₅ --CO--; or an aromatic or heteroaromatic ringwhich is unsubstituted or substituted by halogen, --CN, --NO₂, R₆ R₇ R₈Si--, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃(M₁)_(1/2), C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂ hydroxyalkyl, C₁-C₄ cyanoalkyl, C₃ -C₆ cycloalkyl, C₆ -C₁₂ aryl, C₇ -C₁₂ araLkyl, C₃ -C₆heterocycloalkyl, C₃ -C₁₂ heteroaryl, C₄ -C₂ heteroaralkyl or R₁₃ --X₁-- can be fused to adjacent carbon atoms; X and X₁ are eachindependently of the other --O--, --S--, --CO--, --SO--, --SO₂ --,--O--C(O)--, --C(O)--O--, --C(O)--NR₅ --, --NR₁₀ --C(O)--, --SO₂ --O--or --O--SO₂ --; and R₁, R₂ and R₃ are each independently of one anotherC₁ -C₆ alkyl, C₁ -C₆ perfluoroalkyl, phenyl or benzyl; M is an alkalimetal and M₁ is an alkaline earth metal; R₄ and R₁₃ are eachindependently of the other C₁ -C₁₂ alkyl, C₁ -C₁₂ haloalkyl, C₁ -C₁₂hydroxyalkyl, C₃ -C₈ cycloalkyl, C₆ -C₁₂ aryl or C₇ -C₁₂ aralkyl; R₅ andR₁₀ are each independently of the other hydrogen, C₁ -C₆ alkyl, phenylor benzyl, the alkyl groups in turn being unsubstituted or substitutedby C₁ -C₆ alkoxy or C₃ -C₆ cycloalkyl; R₆, R₇ and R₈ are eachindependently of one another C₁ -C₆ alkyl, C₁ -C₆ perfluoroalkyl, phenylor benzyl; u is 0 or 1;and the alicyclic ring formed with Q₁ may containfurther non-aromatic double bonds; Q₂ is hydrogen, C₁ -C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁ -C₆ alkoxy, halogen, --CN or R₁₁ --X₂ --; R₁₁ is C₁-C₁₂ alkyl, C₁ -C₁₂ halogalkyl, C₁ -C₁₂ hydroxyalkyl, C₃ -C₆ cycloalkyl,C₆ -C₁₂ aryl or C₇ -C₁₂ aralkyl; X₂ is --C(O)--O-- or --C(O)--NR₁₂ --;and R₁₂ is hydrogen, C₁ -C₆ alkyl, phenyl or benzyl;and the cycloalkyl,heterocycloalkyl, aryl, heteroaryl, aralkyl and hetemaralkyl groups areunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, --NO₂, --CNor halogen, and the hetero atoms of the heterocycloalkyl, heteroaryl andheteroaralkyl groups are selected from the group consisting of --O--,--S--, --NR₉ -- and --N═; and R₉ is hydrogen, C₁ -C₆ alkyl, phenyl orbenzyl.
 10. A process according to claim 6, wherein in formula IQ₁ is aradical having at least one carbon atom which, together with the--CH═CQ₂ -- group, forms a 3- to 10-membered alicyclic ring which maycontain a hetero atom selected from the group consisting of silicon,oxygen, nitrogen and sulfur, and which radical is unsubstituted orsubstituted by halogen, --CN, --NO₂, R₁ R₂ R₃ Si--, --COOM, --SO₃ M,--PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2), --PO₃ (M₁)_(1/2), C₁ -C₆alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ hydroxyalkyl, C₁ -C₄ cyanoalkyl, C₃ -C₆cycloalkyl, phenyl, benzyl or R₄ --X--; or an aromatic or heteroaromaticring which is unsubstituted or substituted by halogen, --CN, --NO₂, R₆R₇ R₈ Si--, --COOM, --SO₃ M, --PO₃ M, --COO(M₁)_(1/2), --SO₃ (M₁)_(1/2),--PO₃ (M₁)_(1/2), C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ hydroxyalkyl,C₁ -C₄ cyanoalkyl, C₃ -C₆ cycloalkyl, phenyl, benzyl or R₁₃ --X₁ -- canbe fused to adjacent carbon atoms; R₁, R₂ and R₃ are each independentlyof one another C₁ -C₄ alkyl, C₁ -C₄ perfluoroalkyl, phenyl or benzyl; Mis an alkali metal and M₁ is an alkaline earth metal; R₄ and R₁₃ areeach independently of the other C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆hydroxyalkyl or C₃ -C₆ cycloalkyl; X and X₁ are each independently ofthe other --O--, --S--, --CO--, --SO-- or --SO₂ --; R₆, R₇ and R₈ areeach independently of one another C₁ -C₄ alkyl, C₁ -C₄ perfluoroalkyl,phenyl or benzyl; and Q₂ is hydrogen.
 11. A process according to claim1, wherein the cyclic olefin is a norbornene or norbornene derivative.12. A process according to claim 11, wherein the norbornene derivativeis a compound of formula II ##STR18## wherein X₃ is --CHR₁₆ --, oxygenor sulfur,R₁₄ and R₁₅ are each independently of the other hydrogen,--CN, trifluoromethyl, (CH₃)₃ Si--O--, (CH₃)₃ Si-- or --COOR₁₇ ; and R₁₆and R₁₇ are each independently of the other hydrogen, C₁ -C₁₂ alkyl,phenyl or benzyl.
 13. A process according to claim 11, wherein thenorbornene derivative is a compound of formula III ##STR19## wherein X₄is --CHR₁₉ --, oxygen or sulfur;R₁₉ is hydrogen, C₁ -C₁₂ alkyl, phenylor benzyl; and R₁₈ is hydrogen, C₁ -C₆ alkyl or halogen.
 14. A processaccording to claim 11, wherein the norbomene derivative is a compound offormula IV ##STR20## wherein X₅ is --CHR₂₂ --, oxygen or sulfur,R₂₂ ishydrogen, C₁ -C₁₂ alkyl, phenyl or benzyl; R₂₀ and R₂₁ are eachindependently of the other hydrogen, CN, trifluoromethyl, (CH₃)₃Si--O--, (CH₃)₃ Si-- or --COOR₂₃ ; and R₂₃ is hydrogen, C₁ -C₁₂ alkyl,phenyl or benzyl.
 15. A process according to claim 11, wherein thenorbomene derivative is a compound of formula V ##STR21## wherein X₆ is--CHR₂₄ --, oxygen or sulfur,R₂₄ is hydrogen, C₁ -C₁₂ alkyl, phenyl orbenzyl; Y is oxygen or ##STR22## and R₂₅ is hydrogen, methyl, ethyl orphenyl.
 16. A process according to claim 1, wherein the molybdenum (VI)and tungsten (VI) compounds are those which contain one metal atom ortwo metal atoms linked through a single, double or triple bond.
 17. Aprocess according to claim 1, wherein two to four metal-ligand bonds arepresent as methyl groups or monosubstituted methyl groups lackingβ-hydrogen atoms and which is bonded to the metal atom.
 18. A processaccording to claim 1, wherein the methyl group or monosubstituted methylgroup without β-hydrogen atoms bonded to the metal atom has the formulaVII

    --CH.sub.2 --R                                             (VII),

wherein R is H, --CF₃, --CR₂₆ R₂₇ R₂₈, --SiR₂₉ R₃₀ R₃₁, unsubstituted orC₁ -C₆ alkyl- or C₁ -C₆ alkoxy-substituted C₆ -C₁₆ aryl or C₄ -C₁₅heteroaryl containing 1 to 3 hetero atoms selected from the groupconsisting of O, S and N; and R₂₆, R₂₇ and R₂₈ are each independently ofone another C₁ -C₁₀ alkyl which is unsubstituted or substituted by C₁-C₁₀ alkoxy, or R₂₆ and R₂₇ have this meaning and R₂₈ is C₆ -C₁₀ aryl orC₄ -C₉ heteroaryl which is unsubstituted or substituted by C₁ -C₆ alkylor C₁ -C₆ alkoxy; and R₂₉, R₃₀ and R₃₁ are each independently of oneanother C₁ -C₆ alkyl, C₅ -- or C₆ cycloalkyl, or unsubstituted phenyl orbenzyl or phenyl or benzyl each substituted by C₁ -C₆ alkyl or C₁ -C₆alkoxy.
 19. A process according to claim 18, wherein the group R informula VII is H, --C(CH₃)₃, --C(CH₃)₂ C₆ H₅, unsubstituted phenyl orphenyl which is substituted by methyl, ethyl, methoxy or ethoxy, --CF₃,or --Si(CH₃)₃.
 20. A process according to claim 1, wherein the other 1to 4 valencies of the Mo (VI) and W (VI) atoms can be saturated withidentical or different ligands selected from the group consisting of ═O,═N--R₃₃, secondary amines containing 2 to 18 carbon atoms, R₃₂ O-- orR₃₂ S--, halogen, cyclopentadienyl or bridged biscylopentadienyl,tridentate monoanionic ligands, neutral ligands, wherein the R₃₂substituents independently of each other are unsubstituted or C₁ -C₆alkoxy- or halogen-substituted linear or branched C₁ -C₁₈ alkyl, C₅ - orC₆ cycloalkyl which is unsubsitituted or substituted by C₁ -C₆ alkyl, C₁-C₆ alkoxy or halogen, or phenyl which is unsubstituted or substitutedby C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethylor halogen, or benzyl which is unsubstituted or substituted by C₁ -C₆alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl orhalogen, or phenylethyl; and R₃₃ is unsubstituted or C₁ -C₆alkoxy-subsitituted linear or branched C₁ -C₁₈ alkyl, C₅ - or C₆cycloalkyl which is unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁-C₆ -alkyl)amino, di(C₁ -C₆ alkyl)amino-C₁ -C₃ alkyl or halogen, orbenzyl or phenylethyl each of which is unsubstituted or substituted byC₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl orhalogen.
 21. A process according to claim 1, wherein the molybdenum andtungsten compounds are compounds of formulae VIII, VIIIa, VIIlb andVIIIc, ##STR23## wherein Me is Mo(VI) or W(VI), at least two of thesubstituents R₃₉ to R₄₄ are a radical --CH₂ --R of formula VII, R is H,--CF₃, --CR₂₆ R₂₇ R₂₈, --SiR₂₉ R₃₀ R₃₁, unsubstituted or C₁ -C₆ alkyl-or C₁ -C₆ alkoxy-substituted C₆ -C₁₆ aryl or C₄ -C₁₅ heteroarylcontaining 1 to 3 hetero atoms selected from the group consisting of O,S and N;R₂₆, R₂₇ and R₂₈ are each independently of the other C₁ -C₁₀alkyl which is unsubstituted or substituted by C₁ -C₁₀ alkoxy, or R₂₆and R₂₇ have this meaning and R₂₈ is C₆ -C₁₀ aryl or C₄ -C₉ heteroarylwhich is unsubstituted or substituted by C₁ -C₆ alkyl or C₁ -C₆ alkoxy;and R₂₉, R₃₀ and R₃₁ are each independently of one another C₁ -C₆ alkyl,C₅ - or C₆ cycloalkyl, or unsubstituted or C₁ -C₆ alkyl- or C₁ -C₆alkoxy-substituted phenyl or benzyl; two each of the remainingsubstituents R₃₉ to R₄₄ are ═O or ═N--R₃₃, and R₃₃ is unsubstituted orC₁ -C₆ alkoxy-substituted linear or branched C₁ -C₁₈ alkyl,unsubstituted or C₁ -C₆ alkyl-, C₁ -C₆ alkoxy- or halogen-substitutedC₅ - or C₆ cycloalkyl, unsubstituted phenyl or phenyl which issubstituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxymethyl, C₁ -C₆alkoxyethyl or halogen, or benzyl or phenylethyl each of which isunsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen; and/or the remainingsubstituents R₃₉ to R₄₄ are secondary amino containing 2 to 18 carbonatoms, R₃₂ O-- or R₃₂ S-, halogen, cyclopentadienyl or bridgedbiscylopentadienyl wherein the R₃₂ substituents are each independentlyof the other unsubstituted or C₁ -C₆ alkoxy- or halogen-substitutedlinear or branched C₁ -C₁₈ alkyl, unsubstituted or C₁ -C₆ alkyl-, C₁ -C₆alkoxy or halogen-substituted C₅ - or C₆ cycloalkyl, unsubstitutedphenyl or phenyl which is substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁-C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl, di(C₁ -C₆ -alkyl)amino, di(C₁ -C₆-alkyl)amino-C₁ C₃ alkyl or halogen, or benzyl or phenylethyl each ofwhich is unsubstituted or substituted by C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁-C₆ alkoxymethyl, C₁ -C₆ alkoxyethyl or halogen.
 22. A process accordingto claim 21, which comprises using molybdenum and tungsten compounds offormula VIII, whereina) R₃₉ to R₄₄ are a radical of formula VII --CH₂--R, or b) R₃₉ and R₄₀ are a radical of formula VII --CH₂ --R, R₄₁ andR₄₂ together are a radical ═N--R₃₃, and R₄₃ and R₄₄ together are R₃₂--O-- or halogen, or c) R₄₃ and R₄₄ together and R₄₁ and R₄₂ togetherare the radical ═N--R₃₃, and R₃₉ and R₄₀ are a radical of formula VII--CH₂ --R, wherein R, R₃₂ and R₃₃ are as defined in claim
 21. 23. Aprocess according to claim 21, which comprises using molybdenum andtungsten compounds of formulae IX, IXa or IXb, ##STR24## wherein Me isMo(VI) or W(VI),R is H, --C(CH₃)₃, --C(CH₃)₂ --C₆ H₅, --C₆ H₅ or --Si(C₁-C₄ alkyl)₃, R₃₃ is phenyl or phenyl which is substituted by 1 to 3 C₁-C₄ alkyl or C₁ -C₄ aloxy groups, R₄₁ is unsubstituted orfluoro-substituted linear or branched C₁ -C₄ alkoxy, and R₄₂ has thesame meaning as R₄₁ or is F, Cl or Br.
 24. A process according to claim23, wherein R₄₁ is branched alkoxy or branched alkoxy which may bepartially or completely fluorinated.
 25. A process according to claim23, wherein R₄₂ is chloro.
 26. A process according to claim 21,whereinthe molybdenum and tungsten compounds are selected from the groupconsisting of:Mo₂ CH₂ Si(CH₃)₃ !₆, W(═N--C₆ H₅) OCH(CH₃)₂ !(Cl) CH₂Si(CH₃)₃ !₂, W(═N--C₆ H₅) OCH(CF₃)₂ !₂ CH₂ Si(CH₃)₃ !₂,Mo(═N--3,5-diisopropylC₆ H₃)₂ CH₂ C(CH₃)₂ --C₆ H₅ !₂,Mo(═N--3,5-diisopropylC₆ H₃)₂ CH₂ --C₆ H₅ !₂, Mo(═N--3,5-dimethylC₆ H₃)₂CH₂ --C₆ H₅ !₂, W(═NC₆ H₅) CH₂ Si(CH₃)₃ !Cl or Mo(═N--3,5-dimethylC₆H₃)₂ (CH₃)₂ (tetrahydrofuran).
 27. A process for the photocatalyticpolymerisation of a cyclic olefin or at least two different cyclicolefins in the presence of a metal compound as catalyst, which processcomprisesa) initially irradiating the cycloolefin or cycloolefins in thepresence of a catalytic amount of at least one thermostable molybdenum(VI) or tungsten (VI) compound according to claim 1; or irradiating acatalytic amount of at least one thermostable molybdenum (VI) ortungsten (VI) compound according to claim 1, without a solvent or in aninert solvent, and then mixing the catalyst with at least onecycloolefin; and b) terminating the polymerisation using heat.
 28. Aprocess according to claim 1, wherein the molybdenum (VI) and tungsten(VI) compounds are used in an amount of 0.001 to 20 mol %, based on theamount of the cycloolefin.
 29. A composition comprising (a) a cyclicolefin or at least two different cyclic olefins and (b) a catalyticallyeffective amount of at least one thermostable molybdenum (VI) andtungsten (VI) compound which contains at least two methyl groups or twomonosubstituted methyl groups lacking β-hydrogen atoms in thiesubstituent which are bonded to the metal atom.